Substitution of alpha-nitrobenzylic compounds by a methoxycarbonyl group, either on the phenyl ring (p-methoxycarbonyl-alpha-nitrotoluene Ic) either in the aliphatic chain (methyl-alpha-nitrophenylacetate Id) increases the yield in the corresponding oxime during electroreduction of this substrates. Subsequent chemical oxidation, with iodine, of the hydroxylamine which is simultaneously formed leads to high oxime yields (80 to 98%).